title: Quaternary centres bearing nitrogen (α-tertiary amines) as products of molecular rearrangements.
abstract: Quaternary centres bearing a nitrogen substituent (α-tertiary amines and their derivatives) are found in a variety of bioactive molecules but pose a major challenge in synthesis, particularly when enantiomeric purity is required. Approaches comparable to those used for tertiary alcohols are typically hampered by the poor electrophilicity of imines, requiring powerful nucleophiles that may also act as bases. A set of powerful alternative approaches make use of the rearrangement of readily available precursors, often (but not always) with formation of a new tertiary carbon to nitrogen bond. In this Feature Article we review the scope, limitations and specificities of some of these rearrangements in order to illuminate their synthetic potential.
authors.affiliation: School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, United Kingdom. j.p.Clayden@man.ac.uk
authors.forename: Jonathan
authors.initials: J
authors.lastname: Clayden
authors.forename: Morgan
authors.initials: M
authors.lastname: Donnard
authors.forename: Julien
authors.initials: J
authors.lastname: Lefranc
authors.forename: Daniel J
authors.initials: DJ
authors.lastname: Tetlow
mesh_terms: D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D000588:Amines